Method for the production of monohydroxy-functionalized dialkylphosphinic acids, esters, and salts using ethylene oxide, and use thereof

ABSTRACT

A method for producing monohydroxy-functionalized dialkylphosphinic acids, esters, and salts, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to obtain an alkylphosphonous acid, the salt or ester (II) thereof, b) the obtained alkylphosphonous acid, the salt or ester (II) thereof is reacted with alkylene oxides of formula (V) in the presence of a catalyst B to obtain a monofunctionalized dialkylphosphinic acid derivative (III), catalyst A represents transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and catalyst B is a Lewis acid.

This invention relates to a method for producingmonohydroxy-functionalized dialkylphosphinic acids, esters and salts bymeans of ethylene oxide and to their use

Hitherto there are no methods in existence for producingmonohydroxy-functionalized dialkylphosphinic acids, esters and saltsthat are available economically and on a large industrial scale and moreparticularly enable a high space-time yield to be achieved. Nor arethere any methods that are sufficiently effective without unwelcomehalogen compounds as starting materials, nor any where the end productsare easy to obtain or isolate and obtainable in a specific and desirablemanner under controlled reaction conditions (transesterification forexample).

We have found that this object is achieved by a method for producingmonohydroxy-functionalized dialkylphosphinic acids, esters and salts,which comprises

a) reacting a phosphinic acid source (I)

with olefins (IV)

in the presence of a catalyst A to form an alkylphosphonous acid, saltor ester (II)

b) reacting the resulting alkylphosphonous acid, salt or ester (II) withan alkylene oxide (V)

in the presence of a catalyst B and a base to form themonohydroxy-functionalized dialkylphosphinic acid derivative (III)

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ are identical or different and areeach independently H, C₁-C₁₈-alkyl, C₆-C₁₈-aryl, C₆-C₁₈-aralkyl,C₆-C₁₈-alkylaryl, CN, CHO, OC(O)CH₂CN, CH(OH)C₂H₅, CH₂CH(OH)CH₃,9-anthracene, 2-pyrrolidone, (CH₂)_(m)OH, (CH₂)_(m)NH₂, (CH₂)_(m)NCS,(CH₂)_(m)NC(S)NH₂, (CH₂)_(m)SH, (CH₂)_(m)S-2-thiazoline, (CH₂)_(m)SiMe₃,C(O)R⁹, (CH₂)_(m)C(O)R⁹, CH═CHR⁹ and/or CH═CH—C(O)R⁹ and where R⁹ isC₁-C₈-alkyl or C₆-C₁₈-aryl and m is an integer from 0 to 10 and X is H,C₁-C₁₈-alkyl, C₆-C₁₈-aryl, C₆-C₁₈-aralkyl, C₆-C₁₈-alkylaryl,(CH₂)_(k)OH, CH₂—CHOH—CH₂OH, (CH₂)_(k)O(CH₂)_(k)H,(CH₂)_(k)—CH(OH)—(CH₂)_(k)H, (OH₂—CH₂O)_(k)H, (CH₂—C[CH₃]HO)_(k)H,(CH₂—C[CH₃]HO)_(k)(CH₂—CH₂O)_(k)H, (CH₂—CH₂O)_(k)(CH₂—C[CH₃]HO)H,(CH₂—CH₂O)_(k)-alkyl, (CH₂—C[CH₃]HO)_(k)-alkyl,(CH₂—C[CH₃]HO)_(k)(CH₂—CH₂O)_(k)-alkyl,(CH₂—CH₂O)_(k)(CH₂—C[CH₃]HO)O-alkyl, (CH₂)_(k)—CH═CH(CH₂)_(k)H,(CH₂)_(k)NH₂ and/or (CH₂)_(k)N[(CH₂)_(k)H]₂, where k is an integer from0 to 10, and/or Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn,Cu, Ni, Li, Na, K, H and/or a protonated nitrogen base and the catalystA comprises transition metals and/or transition metal compounds and/orcatalyst systems composed of a transition metal and/or transition metalcompound and at least one ligand, and the catalyst B comprises a Lewisacid.

Preferably, the monohydroxy-functionalized dialkylphosphinic acid, itssalt or ester (III) obtained after step b) is subsequently reacted in astep c) with metal compounds of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn,Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogen base to form thecorresponding monohydroxy-functionalized dialkylphosphinic acid salts(III) of these metals and/or of a nitrogen compound.

Preferably, the alkylphosphonous acid, salt or ester (II) obtained afterstep a) and/or the monohydroxy-functionalized dialkylphosphinic acid,salt or ester (III) obtained after step b) and/or the particularresulting reaction solution thereof are esterified with an alkyleneoxide or an alcohol M-OH and/or M′-OH, and the respectively resultingalkylphosphonous ester (II) and/or monohydroxy-functionalizeddialkylphosphinic ester (III) are subjected to the further reactionsteps b) or c).

Preferably, the groups C₆-C₁₈-aryl, C₆-C₁₈-aralkyl and C₆-C₁₈-alkylarylare substituted with SO₃X₂, —C(O)CH₃, OH, CH₂OH, CH₃SO₃X₂, PO₃X₂, NH₂,NO₂, OCH₃, SH and/or OC(O)CH₃.

Preferably, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ are identical or differentand are each independently H, methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, tert-butyl and/or phenyl.

Preferably, X is H, Ca, Mg, Al, Zn, Ti, Fe, Ce, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, ethylene glycol,propyl glycol, butyl glycol, pentyl glycol, hexyl glycol, allyl and/orglycerol.

Preferably m=1 to 10 and k=2 to 10.

Preferably, the catalyst system A is formed by reaction of a transitionmetal and/or of a transition metal compound and at least one ligand.

Preferably, the transition metals and/or transition metal compoundscomprise such from the seventh and eighth transition groups.

Preferably, the transition metals and/or transition metal compoundscomprise rhodium, nickel, palladium, platinum, ruthenium.

Preferably, the catalyst B comprises Lewis acids.

Preferably, the bases used in process step b) are metals, metalhydrides, organo-metal compounds and metal alkoxides.

Preferably, the alkylene oxides (V) comprise ethylene oxide,1,2-propylene oxide, 1,2-epoxybutane, 1,2-epoxyethylbenzene,(2,3-epoxypropyl)benzene, 2,3-epoxy-1-propanol and/or3,4-epoxy-1-butene.

Preferably, the alcohol of the general formula M-OH comprises linear orbranched, saturated and unsaturated, monohydric organic alcohols havinga carbon chain length of C₁-C₁₈ and the alcohol of the general formulaM′-OH comprises linear or branched, saturated and unsaturated polyhydricorganic alcohols having a carbon chain length of C₁-C₁₈.

The present invention also provides for the use ofmonohydroxy-functionalized dialkylphosphinic acids, esters and salts(III) obtained according to one or more of claims 1 to 7 as anintermediate for further syntheses, as a binder, as a crosslinker oraccelerant to cure epoxy resins, polyurethanes and unsaturated polyesterresins, as polymer stabilizers, as crop protection agents, as atherapeutic or additive in therapeutics for humans and animals, as asequestrant, as a mineral oil additive, as a corrosion control agent, inwashing and cleaning applications and in electronic applications.

The present invention likewise provides for the use ofmonohydroxy-functionalized dialkylphosphinic acids, salts and estersobtained according to one or more of claims 1 to 7 as a flame retardant,more particularly as a flame retardant for clearcoats and intumescentcoatings, as a flame retardant for wood and other cellulosic products,as a reactive and/or nonreactive flame retardant for polymers, in themanufacture of flame-retardant polymeric molding materials, in themanufacture of flame-retardant polymeric molded articles and/or forflame-retardant finishing of polyester and cellulose straight and blendfabrics by impregnation.

The present invention additionally provides a flame-retardantthermoplastic or thermoset polymeric molding material containing 0.5% to45% by weight of monohydroxy-functionalized dialkylphosphinic acids,salts or esters obtained according to one or more of claims 1 to 7, 0.5%to 99% by weight of thermoplastic or thermoset polymer or mixturesthereof, 0% to 55% by weight of additives and 0% to 55% by weight offiller or reinforcing materials, wherein the sum total of the componentsis 100% by weight.

Lastly, the invention also provides flame-retardant thermoplastic orthermoset polymeric molded articles, films, threads and fiberscontaining 0.5% to 45% by weight of monohydroxy-functionalizeddialkylphosphinic acids, salts or esters (III) obtained according to oneor more of claims 1 to 7, 0.5% to 99% by weight of thermoplastic orthermoset polymer or mixtures thereof, 0% to 55% by weight of additivesand 0% to 55% by weight of filler or reinforcing materials, wherein thesum total of the components is 100% by weight.

All the aforementioned reactions can also be carried out in stages;similarly, the various processing steps can also utilize the respectiveresulting reaction solutions.

Preferably, the monohydroxy-functionalized dialkylphosphinic acidcomprises 2-(ethylhydroxyphosphinyl)-1-hydroxyethane,2-(propylhydroxyphosphinyl)-1-hydroxyethane,2-(i-propylhydroxyphosphinyl)-1-hydroxyethane,2-(butylhydroxyphosphinyl)-1-hydroxyethane,2-(sec-butylhydroxyphosphinyl)-1-hydroxyethane,2-(i-butylhydroxyphosphinyl)-1-hydroxyethane,2-(2-phenylethylhydroxyphosphinyl)-1-hydroxyethane,2-(ethylhydroxyphosphinyl)-1-methyl-1-hydroxyethane,2-(propylhydroxyphosphinyl)-1-methyl-1-hydroxyethane,2-(i-propylhydroxyphosphinyl)-1-methyl-1-hydroxyethane,2-(butylhydroxyphosphinyl)-1-methyl-1-hydroxyethane,2-(sec-butylhydroxyphosphinyl)-1-methyl-1-hydroxyethane,2-(i-butylhydroxyphosphinyl)-1-methyl-1-hydroxyethane,2-(2-phenylethylhydroxyphosphinyl)-1-methyl-1-hydroxyethane.

Preferably, the monohydroxy-functionalized dialkylphosphinic estercomprises methyl, ethyl; i-propyl; butyl, phenyl; 2-hydroxyethyl,2-hydroxypropyl, 3-hydroxpropyl, 4-hydroxybutyl and/or2,3-dihydroxypropyl ester of the aforementionedmonohydroxy-functionalized dialkylphosphinic acids.

Preferably, the monohydroxy-functionalized dialkylphosphinic saltcomprises an aluminum(III), calcium(II), magnesium(II), cerium(III),titanium(IV) and/or zinc(II) salt of the aforementionedmonohydroxy-functionalized dialkylphosphinic acids.

Preferably, the transition metals for catalyst A comprise elements ofthe seventh and eighth transition groups (a metal of group 7, 8, 9 or10, in modern nomenclature), for example rhenium, ruthenium, cobalt,rhodium, iridium, nickel, palladium, platinum.

Preference for use as source of the transition metals and transitionmetal compounds is given to their metal salts. Suitable salts are thoseof mineral acids containing the anions fluoride, chloride, bromide,iodide, fluorate, chlorate, bromate, iodate, fluorite, chlorite,bromite, iodite, hypofluorite, hypochlorite, hypobromite, hypoiodite,perfluorate, perchlorate, perbromate, periodate, cyanide, cyanate,nitrate, nitride, nitrite, oxide, hydroxide, borate, sulfate, sulfite,sulfide, persulfate, thiosulfate, sulfamate, phosphate, phosphite,hypophosphite, phosphide, carbonate and sulfonate, for examplemethanesulfonate, chlorosulfonate, fluorosulfonate,trifluoromethanesulfonate, benzenesulfonate, naphthylsulfonate,toluenesulfonate, t-butylsulfonate, 2-hydroxypropanesulfonate andsulfonated ion exchange resins; and/or organic salts, for exampleacetylacetonates and salts of a carboxylic acid having up to 20 carbonatoms, for example formate, acetate, propionate, butyrate, oxalate,stearate and citrate including halogenated carboxylic acids having up to20 carbon atoms, for example trifluoroacetate, trichloroacetate.

A further source of the transition metals and transition metal compoundsis salts of the transition metals with tetraphenylborate and halogenatedtetraphenylborate anions, for example perfluorophenylborate.

Suitable salts similarly include double salts and complex saltsconsisting of one or more transition metal ions and independently one ormore alkali metal, alkaline earth metal, ammonium, organic ammonium,phosphonium and organic phosphonium ions and independently one or moreof the abovementioned anions. Examples of suitable double salts areammonium hexachloropalladate and ammonium tetrachloropalladate.

Preference for use as a source of the transition metals is given to thetransition metal as an element and/or a transition metal compound in itszerovalent state.

Preferably, the transition metal salt is used as a metal, or as an alloywith further metals, in which case boron, zirconium, tantalum, tungsten,rhenium, cobalt, iridium, nickel, palladium, platinum and/or gold ispreferred here. The transition metal content in the alloy used ispreferably 45-99.95% by weight.

Preferably, the transition metal is used in microdisperse form (particlesize 0.1 mm-100 μm).

Preferably, the transition metal is used supported on a metal oxide suchas, for example, alumina, silica, titanium dioxide, zirconium dioxide,zinc oxide, nickel oxide, vanadium oxide, chromium oxide, magnesiumoxide, Celite®, diatomaceous earth, on a metal carbonate such as, forexample, barium carbonate, calcium carbonate, strontium carbonate, on ametal sulfate such as, for example, barium sulfate, calcium sulfate,strontium sulfate, on a metal phosphate such as, for example, aluminumphosphate, vanadium phosphate, on a metal carbide such as, for example,silicone carbide, on a metal aluminate such as, for example, calciumaluminate, on a metal silicate such as, for example, aluminum silicate,chalks, zeolites, bentonite, montmorillonite, hectorite, onfunctionalized silicates, functionalized silica gels such as, forexample, SiliaBond®, QuadraSil™, on functionalized polysiloxanes suchas, for example, Deloxan®, on a metal nitride, on carbon, activatedcarbon, mullite, bauxite, antimonite, scheelite, perovskite,hydrotalcite, heteropolyanions, on functionalized and unfunctionalizedcellulose, chitosan, keratin, heteropolyanions, on ion exchangers suchas, for example, Amberlite™, Amberjet™, Ambersep™, Dowex®, Lewatit®,ScavNet®, on functionalized polymers such as, for example, Chelex®,QuadraPure™, Smopex®, PolyOrgs®, on polymer-bound phosphanes, phosphaneoxides, phosphinates, phosphonates, phosphates, amines, ammonium salts,amides, thioamides, ureas, thioureas, triazines, imidazoles, pyrazoles,pyridines, pyrimidines, pyrazines, thiols, thiol ethers, thiol esters,alcohols, alkoxides, ethers, esters, carboxylic acids, acetates,acetals, peptides, hetarenes, polyethyleneimine/silica and/ordendrimers.

Suitable sources for the metal salts and/or transition metals likewisepreferably include their complex compounds. Complex compounds of themetal salts and/or transition metals are composed of the metalsalts/transition metals and one or more complexing agents. Suitablecomplexing agents include for example olefins, diolefins, nitriles,dinitriles, carbon monoxide, phosphines, diphosphines, phosphites,diphosphites, dibenzylideneacetone, cyclopentadienyl, indenyl orstyrene. Suitable complex compounds of the metal salts and/or transitionmetals may be supported on the abovementioned support materials.

The proportion in which the supported transition metals mentioned arepresent is preferably in the range from 0.01% to 20% by weight, morepreferably from 0.1% to 10% by weight and even more preferably from 0.2%to 5% by weight, based on the total mass of the support material.

Suitable sources for transition metals and transition metal compoundsinclude for example palladium, platinum, nickel, rhodium; palladiumplatinum, nickel or rhodium, on alumina, on silica, on barium carbonate,on barium sulfate, on calcium carbonate, on strontium carbonate, oncarbon, on activated carbon; platinum-palladium-gold alloy,aluminum-nickel alloy, iron-nickel alloy, lanthanide-nickel alloy,zirconium-nickel alloy, platinum-iridium alloy, platinum-rhodium alloy;Raney® nickel, nickel-zinc-iron oxide; palladium(II) chloride,palladium(II) bromide, palladium(II) iodide, palladium(II) fluoride,palladium(II) hydride, palladium(II) oxide, palladium(II) peroxide,palladium(Il) cyanide, palladium(II) sulfate, palladium(II) nitrate,palladium(II) phosphide, palladium(II) boride, palladium(II) chromiumoxide, palladium(II) cobalt oxide, palladium(II) carbonate hydroxide,palladium(II) cyclohexane butyrate, palladium(II) hydroxide,palladium(II) molybdate, palladium(II) octanoate, palladium(II) oxalate,palladium(II) perchlorate, palladium(II) phthalocyanine, palladium(II)5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, palladium(II)sulfamate, palladium(II) perchlorate, palladium(II) thiocyanate,palladium(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate), palladium(II)propionate, palladium(II) acetate, palladium(Il) stearate, palladium(II)2-ethylhexanoate, palladium(II) acetylacetonate, palladium(II)hexafluoroacetylacetonate, palladium(II) tetrafluoroborate,palladium(II) thiosulfate, palladium(II) trifluoroacetate, palladium(II)phthalocyaninetetrasulfonic acid tetrasodium salt, palladium(II) methyl,palladium(II) cyclopentadienyl, palladium(II) methylcyclopentadienyl,palladium(II) ethylcyclopentadienyl, palladium(II)pentamethylcyclopentadienyl, palladium(II)2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, palladium(II)5,10,15,20-tetraphenyl-21H,23H-porphine,bis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), palladium(II)2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, palladium(II)2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, palladium(II)5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)-propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenylsulfinyl)ethane,1,3-bis(2,6-diisopropylphenyl)-imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylaminomethyl)ferrocene, allyl, bis(diphenylphosphino)-butane,(N-succinimidyl)bis(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo-[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 1,2-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;

nickel(II) chloride, nickel(II) bromide, nickel(II) iodide, nickel(II)fluoride, nickel(II) hydride, nickel(II) oxide, nickel(II) peroxide,nickel(II) cyanide, nickel(II) sulfate, nickel(II) nitrate, nickel(II)phosphide, nickel(II) boride, nickel(II) chromium oxide, nickel(II)cobalt oxide, nickel(II) carbonate hydroxide, nickel(II) cyclohexanebutyrate, nickel(II) hydroxide, nickel(II) molybdate, nickel(II)octanoate, nickel(II) oxalate, nickel(II) perchlorate, nickel(II)phthalocyanine, nickel(II)5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, nickel(II)sulfamate, nickel(II) perchlorate, nickel(II) thiocyanate, nickel(II)bis(2,2,6,6-tetramethyl-3,5-heptanedionate), nickel(II) propionate,nickel(II) acetate, nickel(II) stearate, nickel(II) 2-ethylhexanoate,nickel(II) acetylacetonate, nickel(II) hexafluoroacetylacetonate,nickel(II) tetrafluoroborate, nickel(II) thiosulfate, nickel(II)trifluoroacetate, nickel(II) phthalocyaninetetrasulfonic acidtetrasodium salt, nickel(II) methyl, nickel(II) cyclopentadienyl,nickel(II) methylcyclopentadienyl, nickel(II) ethylcyclopentadienyl,nickel(II) pentamethylcyclopentadienyl, nickel(II)2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, nickel(II)5,10,15,20-tetraphenyl-21H,23H-porphine, nickel(II)bis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), nickel(II)2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, nickel(II)2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, nickel(II)5,10,15,20-tetrakis-(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenylsulfinyl)-ethane,1,3-bis(2,6-diisopropylphenyl)imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylaminomethyl)ferrocene, allyl, bis(diphenylphosphino)butane,(N-succinimidyl)bis(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)-ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)-phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 1,2-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;

platinum(II) chloride, platinum(II) bromide, platinum(II) iodide,platinum(II) fluoride, platinum(II) hydride, platinum(II) oxide,platinum(II) peroxide, platinum(II) cyanide, platinum(II) sulfate,platinum(II) nitrate, platinum(II) phosphide, platinum(II) boride,platinum(II) chromium oxide, platinum(II) cobalt oxide, platinum(II)carbonate hydroxide, platinum(II) cyclohexane butyrate, platinum(II)hydroxide, platinum(II) molybdate, platinum(II) octanoate, platinum(II)oxalate, platinum(II) perchlorate, platinum(II) phthalocyanine,platinum(II) 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine,platinum(II) sulfamate, platinum(II) perchlorate, platinum(II)thiocyanate, platinum(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate),platinum(II) propionate, platinum(II) acetate, platinum(II) stearate,platinum(II) 2-ethylhexanoate, platinum(II) acetylacetonate,platinum(II) hexafluoroacetylacetonate, platinum(II) tetrafluoroborate,platinum(II) thiosulfate, platinum(II) trifluoroacetate, platinum(II)phthalocyaninetetrasulfonic acid tetrasodium salt, platinum(II) methyl,platinum(II) cyclopentadienyl, platinum(II) methylcyclopentadienyl,platinum(II) ethylcyclopentadienyl, platinum(II)pentamethylcyclopentadienyl, platinum(II)2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, platinum(II)5,10,15,20-tetraphenyl-21H,23H-porphine, platinum(II)bis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), platinum(II)2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, platinum(II)2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, platinum(II)5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenyl-sulfinyl)ethane,1,3-bis(2,6-diisopropylphenyl)-imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylamino-methyl)ferrocene, allyl, bis(diphenylphosphino)-butane,(N-succinimidyl)bis-(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1-bis(diphenylphosphino)-ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)-phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 1,2-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;

rhodium chloride, rhodium bromide, rhodium iodide, rhodium fluoride,rhodium hydride, rhodium oxide, rhodium peroxide, rhodium cyanide,rhodium sulfate, rhodium nitrate, rhodium phosphide, rhodium boride,rhodium chromium oxide, rhodium cobalt oxide, rhodium carbonatehydroxide, rhodium cyclohexane butyrate, rhodium hydroxide, rhodiummolybdate, rhodium octanoate, rhodium oxalate, rhodium perchlorate,rhodium phthalocyanine, rhodium5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, rhodiumsulfamate, rhodium perchlorate, rhodium thiocyanate, rhodiumbis(2,2,6,6-tetramethyl-3,5-heptanedionate), rhodium propionate, rhodiumacetate, rhodium stearate, rhodium 2-ethylhexanoate, rhodiumacetylacetonate, rhodium hexafluoroacetylacetonate, rhodiumtetrafluoroborate, rhodium thiosulfate, rhodium trifluoroacetate,rhodium phthalocyaninetetrasulfonic acid tetrasodium salt, rhodiummethyl, rhodium cyclopentadienyl, rhodium methylcyclopentadienyl,rhodium ethylcyclopentadienyl, rhodium pentamethylcyclopentadienyl,rhodium 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, rhodium5,10,15,20-tetraphenyl-21H,23H-porphine, rhodiumbis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), rhodium2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, rhodium2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, rhodium5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenylsulfinyl)ethane,1,3-bis(2,6-diisopropylphenyl)-imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylaminomethyl)ferrocene, allyl, bis(diphenylphosphino)-butane,(N-succinimidyl)bis(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)-phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 1,2-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;

potassium hexachloropalladate(IV), sodium hexachloropalladate(IV),ammonium hexachloropalladate(IV), potassium tetrachloropalladate(II),sodium tetrachloropalladate(II), ammonium tetrachloropalladate(II),bromo(tri-tert-butylphosphine)-palladium(I) dimer,(2-methylallyl)palladium(II) chloride dimer,bis(dibenzylideneacetone)palladium(0),tris(dibenzylideneacetone)dipalladium(0),tetrakis-(triphenylphosphine)palladium(0),tetrakis(tricyclohexylphosphine)palladium(0),bis[1,2-bis(diphenylphosphine)ethane]palladium(0),bis(3,5,3′,5′-dimethoxydibenzylideneacetone)palladium(0),bis(tri-tert-butylphosphine)palladium(0),meso-tetraphenyltetrabenzoporphinepalladium,tetrakis(methyldiphenylphosphine)-palladium(0),tris(3,3′,3″-phophinidyne-tris(benzenesulfonato)palladium(0) nonasodiumsalt,1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium(0),1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium(0)and the chloroform complex thereof;

allylnickel(II) chloride dimer, ammoniumnickel(II) sulfate,bis(1,5-cyclooctadiene)nickel(0),bis(triphenylphosphine)dicarbonylnickel(0),tetrakis(triphenylphosphine)nickel(0), tetrakis(triphenylphosphite)nickel(0), potassium hexafluoronickelate(IV), potassiumtetracyanonickelate(II), potassium nickel(IV) paraperiodate, dilithiumtetrabromonickelate(II), potassium tetracyanonickelate(II) platinum(IV)chloride, platinum(IV) oxide, platinum(IV) sulfide, potassiumhexachloroplatinate(IV), sodium hexachloroplatinate(IV), ammoniumhexachloroplatinate(IV), potassium tetrachloroplatinate(II), ammoniumtetrachloroplatinate(II), potassium tetracyanoplatinate(II),trimethyl(methylcyclopentadienyl)platinum(IV),cis-diammintetrachloroplatinum(IV), potassiumtrichloro(ethylene)platinate(II), sodium hexahydroxyplatinate(IV),tetraamineplatinum(II) tetrachloroplatinate(II), tetrabutylammoniumhexachloroplatinate(IV), ethylenebis(triphenylphosphine)platinum(0),platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, platinum(0)2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane,tetrakis(triphenylphosphine)platinum(0), platinum octaethylporphyrine,chloroplatinic acid, carboplatin; chlorobis(ethylene)rhodium dimer,hexarhodium hexadecacarbonyl, chloro(1,5-cyclooctadiene)rhodium dimer,chloro(norbomadiene)rhodium dimer, chloro(1,5-hexadiene)rhodium dimer.

The ligands preferably comprise phosphines of the formula (VI)PR¹⁰ ₃  (VI)where the R¹⁰ radicals are each independently hydrogen, straight-chain,branched or cyclic C₁-C₂₀-alkyl, C₆-C₂₀-alkylaryl, C₂-C₂₀-alkenyl,C₂-C₂₀-alkynyl, C₁-C₂₀-carboxylate, C₁-C₂₀-alkoxy, C₂-C₂₀-alkenyloxy,C₂-C₂₀-alkynyloxy, C₂-C₂₀-alkoxycarbonyl, C₁-C₂₀-alkylthio,C₁-C₂₀-alkylsulfonyl, C₁-C₂₀-alkylsulfinyl, silyl and/or theirderivatives and/or phenyl substituted by at least one R¹¹, or naphthylsubstituted by at least one R¹¹. R¹¹ in each occurrence is independentlyhydrogen, fluorine, chlorine, bromine, iodine, NH₂, nitro, hydroxyl,cyano, formyl, straight-chain, branched or cyclic C₁-C₂₀-alkyl,C₁-C₂₀-alkoxy, HN(C₁-C₂₀-alkyl), N(C₁-C₂₀-alkyl)₂, —CO₂—(C₁-C₂₀-alkyl),—CON(C₁-C₂₀-alkyl)₂, —OCO(C₁-C₂₀-alkyl), NHCO(C₁-C₂₀-alkyl),C₁-C₂₀-Acyl, —SO₃M, —SO₂N(R¹²)M, —CO₂M, —PO₃M₂, —AsO₃M₂, —SiO₂M,—C(CF₃)₂OM (M=H, Li, Na or K), where R¹² is hydrogen, fluorine,chlorine, bromine, iodine, straight-chain, branched or cyclicC₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₂-C₂₀-alkynyl, C₁-C₂₀-carboxylate,C₁-C₂₀-alkoxy, C₂-C₂₀-alkenyloxy, C₂-C₂₀-alkynyloxy,C₂-C₂₀-alkoxycarbonyl, C₁-C₂₀-alkylthio, C₁-C₂₀-alkylsulfonyl,C₁-C₂₀-alkylsulfinyl, silyl and/or their derivatives, aryl,C₆-C₂₀-arylalkyl, C₆-C₂₀-alkylaryl, phenyl and/or biphenyl. Preferably,the R¹⁰ groups are all identical.

Suitable phosphines(VI) are for example trimethylphosphine,triethylphosphine, tripropylphosphine, triisopropylphosphine,tributylphosphine, triisobutylphosphine, triisopentylphosphine,trihexylphosphine, tricyclohexylphosphine, trioctylphosphine,tridecylphosphine, triphenylphosphine, diphenylmethylphosphine,phenyldimethylphosphine, tri(o-tolyl)phosphine, tri(p-tolyl)phosphine,ethyldiphenylphosphine, dicyclohexylphenylphosphine,2-pyridyldiphenylphosphine, bis(6-methyl-2-pyridyl)phenylphosphine,tri(p-chlorophenyl)phosphine, tri(p-methoxyphenyl)phosphine,diphenyl(2-sulfonatophenyl)phosphine; potassium, sodium and ammoniumsalts of diphenyl(3-sulfonatophenyl)phosphine,bis(4,6-dimethyl-3-sulfonatophenyl)(2,4-dimethylphenyl)phosphine,bis(3-sulfonatophenyl)phenylphosphines,tris(4,6-dimethyl-3-sulfonatophenyl)phosphines,tris(2-sulfonatophenyl)phosphines, tris(3-sulfonatophenyl)phosphines;2-bis(diphenylphosphinoethyl)trimethylammonium iodide,2′-dicyclohexylphosphino-2,6-dimethoxy-3-sulfonato-1,1′-biphenyl sodiumsalt, trimethyl phosphite and/or triphenyl phosphite.

The ligands more preferably comprise bidentate ligands of the generalformulaR¹⁰ ₂M″-Z-M″R¹⁰ ₂  (VII).

In this formula, each M″ independently is N, P, As or Sb.

M″ is preferably the same in the two occurrences and more preferably isa phosphorus atom.

Each R¹⁰ group independently represents the radicals described underformula (VI). The R¹⁰ groups are preferably all identical.

Z is preferably a bivalent bridging group which contains at least 1bridging atom, preferably from 2 to 6 bridging atoms.

Bridging atoms can be selected from carbon, nitrogen, oxygen, siliconand sulfur atoms. Z is preferably an organic bridging group containingat least one carbon atom. Z is preferably an organic bridging groupcontaining 1 to 6 bridging atoms, of which at least two are carbonatoms, which may be substituted or unsubstituted.

Preferred Z groups are —CH₂—, —CH₂—CH₂—, —CH₂—CH₂—CH₂—,—CH₂—CH(CH₃)—CH₂—, —CH₂—C(CH₃)₂—CH₂—, —CH₂—C(C₂H₅)—CH₂—,—CH₂—Si(CH₃)₂—CH₂—, —CH₂—O—CH₂—, —CH₂—CH₂—CH₂—CH₂—, —CH₂—CH(C₂H₅)—CH₂—,—CH₂—CH(n-Pr)—CH and —CH₂—CH(n-Bu)-CH₂—, substituted or unsubstituted1,2-phenyl, 1,2-cyclohexyl, 1,1′- or 1,2-ferrocenyl radicals,2,2′-(1,1′-biphenyl), 4,5-xanthene and/or oxydi-2,1-phenylene radicals.

Examples of suitable bidentate phosphine ligands (VII) are for example1,2-bis-(dimethylphosphino)ethane, 1,2-bis(diethylphosphino)ethane,1,2-bis(dipropylphosphino)ethane, 1,2-bis(diisopropylphosphino)ethane,1,2-bis(dibutylphosphino)ethane, 1,2-bis(di-tert-butylphosphino)ethane,1,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane;1,3-bis(dicyclohexylphosphino)propane,1,3-bis(diisopropylphosphino)propane,1,3-bis(di-tert-butylphosphino)propane,1,3-bis(diphenylphosphino)propane; 1,4-bis(diisopropylphosphino)butane,1,4-bis(diphenylphosphino)butane; 1,5-bis(dicyclohexylphosphino)pentane;1,2-bis(di-tert-butylphosphino)benzene,1,2-bis(diphenylphosphino)benzene,1,2-bis(dicyclohexylphosphino)benzene,1,2-bis(dicyclopentylphosphino)benzene,1,3-bis(di-tert-butylphosphino)benzene,1,3-bis(diphenylphosphino)benzene,1,3-bis(dicyclohexylphosphino)benzene,1,3-bis(dicyclopentylphosphino)benzene;9,9-dimethyl-4,5-bis(diphenylphosphino)-xanthene,9,9-dimethyl-4,5-bis(diphenylphosphino)-2,7-di-tert-butylxanthene,9,9-dimethyl-4,5-bis(di-tert-butylphosphino)xanthene,1,1′-bis(diphenylphosphino)-ferrocene,2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,2,2′-bis(di-p-tolyl-phosphino)-1,1′-binaphthyl,(oxydi-2,1-phenylene)bis(diphenylphosphine),2,5-(diisopropylphospholano)benzene,2,3-O-isopropropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane,2,2′-bis(di-tert-butylphosphino)-1,1′-biphenyl,2,2′-bis(dicyclohexylphosphino)-1,1′-biphenyl,2,2′-bis(diphenylphosphino)-1,1′-biphenyl,2-(di-tert-butylphosphino)-2′-(N,N-dimethylamino)biphenyl,2-(dicyclohexylphosphino)-2′-(N,N-dimethylamino)biphenyl,2-(diphenylphosphino)-2′-(N,N-dimethylamino)biphenyl,2-(diphenylphosphino)ethylamine, 2-[2-(diphenylphosphino)ethyl]pyridine;potassium, sodium and ammonium salts of1,2-bis(di-4-sulfonatophenylphosphino)benzene,(2,2′-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-4,4′,7,7′-tetrasulfonato-1,1′-binapthyl,(2,2′-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-5,5′-tetrasulfonato-1,1′-biphenyl,(2,2′-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-1,1′-binaphthyl,(2,2′-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-1,1′-biphenyl,9,9-dimethyl-4,5-bis(diphenylphosphino)-2,7-sulfonatoxanthene,9,9-dimethyl-4,5-bis(di-tert-butylphosphino)-2,7-sulfonatoxanthene,1,2-bis(di-4-sulfonatophenylphosphino)benzene,meso-tetrakis(4-sulfonatophenyl)porphine,meso-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphine,meso-tetrakis(3-sulfonatomesityl)porphine,tetrakis(4-carboxy-phenyl)porphine and5,11,17,23-sulfonato-25,26,27,28-tetrahydroxycalix[4]arene.

Moreover, the ligands of the formula (VI) and (VII) can be attached to asuitable polymer or inorganic substrate by the R¹⁰ radicals and/or thebridging group.

The molar transition metal/ligand ratio of the catalyst system is in therange 1:0.01 to 1:100, preferably in the range from 1:0.05 to 1:10 andmore preferably in the range from 1:1 to 1:4.

The reactions in the process stages a), b) and c) preferably take place,if desired, in an atmosphere comprising further gaseous constituentssuch as nitrogen, oxygen, argon, carbon dioxide for example; thetemperature is in the range from −20 to 340° C., more particularly inthe range from 20 to 180° C., and total pressure is in the range from 1to 100 bar.

The products, the transition metal, the transition metal compound, thecatalyst system, the ligand and/or the starting materials are optionallyisolated after the process stages a), b) and c) by distillation orrectification, by crystallization or precipitation, by filtration orcentrifugation, by adsorption or chromatography or other known methods.

According to the present invention, solvents, auxiliaries and any othervolatile constituents are removed by distillation, filtration and/orextraction for example.

The reactions in the process stages a), b) and c) are preferably carriedout, if desired, in absorption columns, spray towers, bubble columns,stirred tanks, trickle bed reactors, flow tubes, loop reactors and/orkneaders.

Suitable mixing elements include for example anchor, blade, MIG,propeller, impeller and turbine stirrers, cross beaters, disperserdisks, hollow (sparging) stirrers, rotor-stator mixers, static mixers,Venturi nozzles and/or mammoth pumps.

The intensity of mixing experienced by the reaction solutions/mixturescorresponds to a rotation Reynolds number in the range from 1 to 1 000000 and preferably in the range from 100 to 100 000.

It is preferable for an intensive commixing of the respective reactantsetc. to be effected by an energy input in the range from 0.080 to 10kW/m³, preferably 0.30-1.65 kW/m³.

During the reaction, the particular catalyst A or B is preferablyhomogeneous and/or heterogeneous in action. Therefore, the particularheterogeneous catalyst is effective during the reaction as a suspensionor bound to a solid phase.

Preferably, the particular catalyst A or B is generated in situ beforethe reaction and/or at the start of the reaction and/or during thereaction.

Preferably, the particular reaction takes place in a solvent as asingle-phase system in homogeneous or heterogeneous mixture and/or inthe gas phase.

When a multi-phase system is used, a phase transfer catalyst may be usedin addition.

The reactions of the present invention can be carried out in liquidphase, in the gas phase or else in supercritical phase. The particularcatalyst A or B is preferably used in the case of liquids in homogeneousform or as a suspension, while a fixed bed arrangement is advantageousin the case of gas phase or supercritical operation.

Suitable solvents are water, alcohols, e.g. methanol, ethanol,isopropanol, n-propanol, n-butanol, isobutanol, tert-butanol, n-amylalcohol, isoamyl alcohol, tert-amyl alcohol, n-hexanol, n-octanol,isooctanol, n-tridecanol, benzyl alcohol, etc. Preference is furthergiven to glycols, e.g. ethylene glycol, 1,2-propanediol,1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol etc.;aliphatic hydrocarbons such as pentane, hexane, heptane, octane, andpetroleum ether, naphtha, kerosene, petroleum, paraffin oil, etc.;aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene,ethylbenzene, diethylbenzene, etc.; halogenated hydrocarbons, such asmethylene chloride, chloroform, 1,2-dichloro-ethane, chlorobenzene,carbon tetrachloride, tetrabromoethylene, etc.; alicyclic hydrocarbons,such as cyclopentane, cyclohexane, and, methylcyclohexane, etc.; ethers,such as anisole (methyl phenyl ether), tert-butyl methyl ether, dibenzylether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether,tetrahydrofuran, triisopropyl ether etc.; glycol ethers, such asdiethylene glycol diethyl ether, diethylene glycol dimethyl ether(diglyme), diethylene glycol monobutyl ether, diethylene glycolmonomethyl ether, 1,2-dimethoxyethane (DME, monoglyme), ethylene glycolmonobutyl ether, triethylene glycol dimethyl ether (triglyme),triethylene glycol monomethyl ether etc.; ketones, such as acetone,diisobutyl ketone, methyl n-propyl ketone; methyl ethyl ketone, methylisobutyl ketone etc.; esters, such as methyl formate, methyl acetate,ethyl acetate, n-propyl acetate, and n-butyl acetate, etc.; carboxylicacids, such as formic acid, acetic acid, propionic acid, butyric acid,etc. One or more of these compounds can be used, alone or incombination.

Suitable solvents also encompass the phosphinic acid sources and olefinsused. These have advantages in the form of higher space-time yield.

It is preferable that the reaction be carried out under the autogenousvapor pressure of the olefin and/or of the solvent.

Preferably, R¹, R², R³ and R⁴ of olefin (IV) are the same or differentand each is independently H, methyl, ethyl, n-propyl, isopropyl n-butyl,isobutyl, tert-butyl and/or phenyl.

Preference is also given to using functionalized olefins such as allylisothiocyanate, allyl methacrylate, 2-allylphenol, N-allylthiourea,2-(allylthio)-2-thiazoline, allyltrimethylsillane, allyl acetate, allylacetoacetate, allyl alcohol, allylamine, allylbenzene, allyl cyanide,allyl cyanoacetate, allylanisole, trans-2-pentenal,cis-2-pentenenitrile, 1-penten-3-ol, 4-penten-1-ol, 4-penten-2-ol,trans-2-hexenal, trans-2-hexen-1-ol, cis-3-hexen-1-ol, 5-hexen-1-ol,styrene, -methylstyrene, 4-methylstyrene, vinyl acetate,9-vinylanthracene, 2-vinylpyridine, 4-vinylpyridine and1-vinyl-2-pyrrolidone.

The partial pressure of the olefin during the reaction is preferably0.01-100 bar and more preferably 0.1-10 bar.

The phosphinic acid/olefin molar ratio for the reaction is preferably inthe range from 1:10 000 to 1:0.001 and more preferably in the range from1:30 to 1:0.01.

The phosphinic acid/catalyst molar ratio for the reaction is preferablyin the range from 1:1 to 1:0.00000001 and more preferably in the rangefrom 1:0.01 to 1:0.000001.

The phosphinic acid/solvent molar ratio for the reaction is preferablyin the range from 1:10 000 to 1:0 and more preferably in the range from1:50 to 1:1.

One method the present invention provides for producing compounds of theformula (II) comprises reacting a phosphinic acid source with olefins inthe presence of a catalyst and freeing the product (II)(alkylphosphonous acid, salts or esters) of catalyst, transition metalor transition metal compound as the case may be, ligand, complexingagent, salts and by-products.

The present invention provides that the catalyst, the catalyst system,the transition metal and/or the transition metal compound are separatedoff by adding an auxiliary 1 and removing the catalyst, the catalystsystem, the transition metal and/or the transition metal compound byextraction and/or filtration.

The present invention provides that the ligand and/or complexing agentis separated off by extraction with auxiliary 2 and/or distillation withauxiliary 2.

Auxiliary 1 is preferably water and/or at least one member of the groupof metal scavengers. Preferred metal scavengers are metal oxides, suchas aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide,zinc oxide, nickel oxide, vanadium oxide, chromium oxide, magnesiumoxide, Celite®, kieselguhr, metal carbonates, such as barium carbonate,calcium carbonate, strontium carbonate, metal sulfates, such as bariumsulfate, calcium sulfate, strontium sulfate, metal phosphates, such asaluminum phosphate, vanadium phosphate, metal carbides, such as siliconecarbide, metal aluminates, such as calcium aluminate, metal silicates,such as aluminum silicate, chalks, zeolites, bentonite, montmorillonite,hectorite, functionalized silicates, functionalized silica gels, such asSiliaBond®, QuadraSil™, functionalized polysiloxanes, such as Deloxan®,metal nitrides, carbon, activated carbon, mullite, bauxite, antimonite,scheelite, perovskite, hydrotalcite, functionalized and unfunctionalizedcellulose, chitosan, keratin, heteropolyanions, ion exchangers, such asAmberlite™, Amberjet™, Ambersep™, Dowex®, Lewatit®, ScavNet®,functionalized polymers, such as Chelex®, QuadraPure™, Smopex®,PolyOrgs®, polymer-bound phosphanes, phosphane oxides, phosphinates,phosphonates, phosphates, amines, ammonium salts, amides, thioamides,urea, thioureas, triazines, imidazoles, pyrazoles, pyridines,pyrimidines, pyrazines, thiols, thiol ethers, thiol esters, alcohols,alkoxides, ethers, esters, carboxylic acids, acetates, acetals,peptides, hetarenes, polyethyleneimine/silicon dioxide, and/ordendrimers.

It is preferable that the amounts added of auxiliary 1 correspond to0.1-40% by weight loading of the metal on auxiliary 1.

It is preferable that auxiliary 1 be used at temperatures of from 20 to90° C.

It is preferable that the residence time of auxiliary 1 be from 0.5 to360 minutes.

Auxiliary 2 is preferably the aforementioned solvent of the presentinvention as are preferably used in process stage a).

The esterification of the monohydroxy-functionalized dialkylphosphinicacid (III) or of the alkylphosphonous acid derivatives (II) and also ofthe phosphinic acid source (I) to form the corresponding esters can beachieved for example by reaction with higher-boiling alcohols byremoving the resultant water by azeotropic distillation, or, by reactionwith epoxides (alkylene oxides).

Preferably, following step a), the alkylphosphonous acid (II) isdirectly esterified with an alcohol of the general formula M-OH and/orM′-OH or by reaction with alkylene oxides, as indicated hereinbelow.

M-OH preferably comprises primary, secondary or tertiary alcohols havinga carbon chain length of C₁-C₁₈. Particular preference is given tomethanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol,tert-butanol, amyl alcohol and/or hexanol.

M′-OH preferably comprises ethylene glycol, 1,2-propylene glycol,1,3-propylene glycol, 1,4-butanediol, 2,2-dimethylpropane-1,3-diol,neopentyl glycol, 1,6-hexane-diol, 1,4-cyclohexanedimethanol, glycerol,trishydroxymethylethane, trishydroxymethylpropane, pentaerythritol,sorbitol, mannitol, α-naphthol, polyethylene glycols, polypropyleneglycols and/or EO-PO block polymers.

Also useful as M-OH and M′-OH are mono- or polyhydric unsaturatedalcohols having a carbon chain length of C₁-C₁₈, for examplen-but-2-en-1-ol, 1,4-butenediol and allyl alcohol.

Also useful as M-OH and M′-OH are reaction products of monohydricalcohols with one or more molecules of alkylene oxides, particularpreference is given to ethylene oxide and 1,2-propylene oxide.Preference is given to 2-methoxyethanol, 2-ethoxyethanol,2-n-butoxyethanol, 2-(2′-ethylhexyloxy)ethanol, 2-n-dodecoxy-ethanol,methyl diglycol, ethyl diglycol, isopropyl diglycol, fatty alcoholpolyglycol ethers and aryl polyglycol ethers.

M-OH and M′-OH are also preferably reaction products of polyhydricalcohols with one or, more molecules of alkylene oxide, moreparticularly diglycol and triglycol and also adducts of 1 to 6 moleculesof ethylene oxide or propylene oxide onto glycerol,trishydroxymethylpropane or pentaerythritol.

Useful M-OH and M′-OH further include reaction products of water withone or more molecules of alkylene oxide. Preference is given topolyethylene glycols and poly-1,2-propylene glycols of various molecularsizes having an average molecular weight of 100-1000 g/mol and morepreferably of 150-350 g/mol.

Preference for use as M-OH and M′-OH is also given to reaction productsof ethylene oxide with poly-1,2-propylene glycols or fatty alcoholpropylene glycols; similarly reaction products of 1,2-propylene oxidewith polyethylene glycols or fatty alcohol ethoxylates. Preference isgiven to such reaction products with an average molecular weight of100-1000 g/mol, more preferably of 150-450 g/mol.

Also useful as M-OH and M′-OH are reaction products of alkylene oxideswith ammonia, primary or secondary amines, hydrogen sulfide, mercaptans,oxygen acids of phosphorus and C₂-C₆ dicarboxylic acids. Suitablereaction products of ethylene oxide with nitrogen compounds aretriethanolamine, methyldiethanolamine, n-butyldiethanolamine,n-dodecyldiethanolamine, dimethylethanolamine,n-butylmethylethanolamine, di-n-butylethanolamine,n-dodecylmethylethanolamine, tetrahydroxyethylethylenediamine orpentahydroxyethyldiethylenetriamine.

Preferred alkylene oxides are ethylene oxide, 1,2-propylene oxide,1,2-epoxy-butane, 1,2-epoxyethylbenzene, (2,3-epoxypropyl)benzene,2,3-epoxy-1-propanol and 3,4-epoxy-1-butene.

Suitable solvents are the solvents mentioned in process step a) and alsothe M-OH and M′-OH alcohols used and alkylene oxides. These offeradvantages in the form of a higher, space-time yield.

The reaction is preferably carried out under the autogenous vaporpressure of the employed alcohol M-OH and M′-OH and alkylene oxideand/or of the solvent.

Preferably, the reaction is carried out at a partial pressure of theemployed alcohol M-OH and M′-OH and alkylene oxide of 0.01-100 bar, morepreferably at a partial pressure of the olefin of 0.1-10 bar.

The reaction is preferably carried out at a temperature in the rangefrom −20 to 340° C. and is more preferably carried out at a temperaturein the range from 20 to 180° C.

The reaction is preferably carried out at a total pressure in the rangefrom 1 to 100 bar.

The reaction is preferably carried out in a molar ratio for the alcoholor alkylene oxide component to the phosphinic acid source (I) oralkylphosphonous acid (II) or monohydroxy-functionalizeddialkylphosphinic acid (III) ranging from 10 000:1 to 0.001:1 and morepreferably from 1000:1 to 0.01:1.

The reaction is preferably carried out in a molar ratio for thephosphinic acid source (I) or alkylphosphonous acid (II) ormonohydroxy-functionalized dialkylphosphinic acid (III) to the solventranging from 1:10 000 to 1:0 and more preferably in a phosphinicacid/solvent molar ratio ranging from 1:50 to 1:1.

Preferred catalysts B as used for process step b) for the reaction ofthe alkyl-phosphonous acid, salts or esters (II) with an alkylene oxide(V) to form the monohydroxy-functionalized dialkylphosphinic acid, saltsand esters (III) are Lewis acids.

Preferred Lewis acids include in particular metal salts, preferablymetal halides, such as fluorides, chlorides, bromides, iodides; andsulfates, sulfonates, haloalkylsulfonates, perhaloalkylsulfonates, forexample fluoroalkylsulfonates or perfluoroalkylsulfonates; haloacetates,perhaloacetates, carboxylates and phosphates such as for example PO₄ ³⁻,HPO₄ ²⁻, H₂PO₄ ⁻; CF₃COO⁻, C₇H₁₅OSO₂ ⁻ or SO₄ ²⁻.

The Lewis acid preferably comprises organic or inorganic metal compoundsin which the cation is selected from the group consisting of scandium,titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc,boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium,rhenium beryllium, gallium, indium, thallium, hafnium, erbium,germanium, tungsten, palladium, thorium and tin. Examples compriseZnBr₂, ZnI₂, ZnCl₂, ZnSO₄, CuCl₂, CuCl, CU(O₃SCF₃)₂, CoCl₂, CoI₂, FeI₂,FeCl₃, FeCl₂, FeCl₂(THF)₂, TiCl₄(THF)₂, TiCl₄, TiCl₃, ClTi(O-i-Propyl)₃,Ti(OMe)₄, Ti(OEt)₄, Ti(O-i-Pr)₄, Ti(O-n-Pr)₄, MnCl₂, ScCl₃, AlCl₃,(C₈H₁₇)AlCl₂, (C₈H₁₇)₂AlCl, (i-C₄H₉)₂AlCl, (C₆H₅)₂AlCl, (C₆H₅)AlCl₂,Al(OMe)₃, Al(OEt)₃, Al(O-i-Pr)₃, Al(O-s-Bu)₃, ReCl₅, ZrCl₄, NbCl₅, VCl₃,CrCl₂, MoCl₅, YCl₃, CdCl₂, LaCl₃, Er(O₃SCF₃)₃, Yb(O₂CCF₃)₃, SmCl₃,TaCl₅.

Also useful are organometallic compounds, such as (C₆H₅)₃SnX where X isCF₃SO₃, CH₃C₆H₄SO₃ and RAlCl₂, R₂AlCl, R₃Al, (RO)₃Al, R₃TiCl, (RO)₄Ti,RSnO₃SCF₃, R₃B and B(OR)₃, where R is selected from H, C₁-C₁₂-alkyl,C₆-C₁₈-aryl, C₆-C₁₈-alkylaryl, C₁-C₇-alkyl-substituted aryl freeradicals and aryl free radicals substituted with cyano-substituted alkylgroups having 1 to 7 carbon atoms, for example PhAlCl₂, Cu(O₃SCF₃)₃.

Preferred bases of the process stage b) are metals, metal hydrides,organometal compounds and metal alkoxides such as for example lithium,lithium hydride, lithium aluminohydride, methyllithium, butyllithium,t-butyllithium, lithium diisopropylamide, sodium, sodium hydride, sodiummethoxide, sodium ethoxide or sodium butoxide, potassium methoxide,potassium ethoxide or potassium butoxide.

The catalyst B is preferably used in amounts of 0.05 to 110 mol % basedon the particular alkylene oxide (V).

The catalyst B is more preferably used in amounts of 0.5 to 50 mol %based on the particular alkylene oxide (V).

The catalyst B is preferably used in amounts of 0.001 to 110 mol %,based on the phosphorus-containing compound.

The catalyst B is more preferably used in amounts of 0.1 to 50 mol %,based on the phosphorus-containing compound.

The base is preferably used in amounts of 0.05 to 150 mol % based on theparticular alkylene oxide (V).

The base is preferably used in amounts of 0.001 to 150 mol %, based onthe phosphorus-containing compound.

The base is preferably metered in at a rate of 0.01 to 500 mol % ofcatalyst per hour, based on the phosphorus-containing compound.

Suitable solvents are those used above in method step a).

The reaction of the alkylphosphonous acids (II) with an alkylene oxide(V) is preferably carried out at a temperature of −100 to 250° C. andmore preferably at −78 to 100° C.

The atmosphere for the reaction with an alkylene oxide (V) preferablyconsists of constituents of the solvent and alkylene oxide (V) to anextent of 50% to 99.9% by weight, preferably 70-95%.

The reaction during the addition of the alkylene oxide (V) is preferablycarried out at a pressure of 1-20 bar.

In a further embodiment of the method, the product mixture obtainedafter process stage a) and/or b) is worked up.

The monohydroxy-functionalized dialkylphosphinic acid or salt (III) canthereafter be converted into further metal salts.

The metal compounds which are used in process stage c) preferablycomprise compounds of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn,Ce, Bi, Sr, Mn, Li, Na, K, more preferably Mg, Ca, Al, Ti, Zn, Sn, Ce,Fe.

Suitable solvents for process stage c) are those used above in processstage a).

The reaction of process stage c) is preferably carried out in an aqueousmedium.

Process stage c) preferably comprises reacting themonohydroxy-functionalized dialkylphosphinic acids, esters and/or alkalimetal salts (III) obtained after process stage b) with metal compoundsof Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe to form themonohydroxy-functionalized dialkylphosphinic acid salts (III) of thesemetals.

The reaction is carried out in a molar ratio ofmonohydroxy-functionalized dialkylphosphinic acid, ester or salt (III)to metal in the range from 8:1 to 1:3 (for tetravalent metal ions ormetals having a stable tetravalent oxidation state), from 6:1 to 1:3(for trivalent metal ions or metals having a stable trivalent oxidationstate), from 4:1 to 1:3 (for divalent metal ions or metals having astable divalent oxidation state) and from 3:1 to 1:4 (for monovalentmetal ions or metals having a stable monovalent oxidation state).

Preferably, monohydroxy-functionalized dialkylphosphinic acid, ester orsalt (III) obtained in process stage b) is converted into thecorresponding dialkylphosphinic acid and the latter is reacted inprocess stage d) with metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ceor Fe to form the monohydroxy-functionalized dialkylphosphinic acidsalts (III) of these metals.

Preferably, monohydroxy-functionalized dialkylphosphinic acid/ester(III) obtained in process stage b) is converted to a dialkylphosphinicacid alkali metal salt and the latter is reacted in process stage d)with metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe to form themonohydroxy-functionalized dialkylphosphinic acid salts (III) of thesemetals.

The metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe for processstage c) preferably comprise metals, metal oxides, hydroxides, oxidehydroxides, borates, carbonates, hydroxocarbonates, hydroxocarbonatehydrates, mixed metal hydroxocarbonates, mixed metal hydroxocarbonatehydrates, phosphates, sulfates, sulfate hydrates, hydroxosulfatehydrates, mixed metal hydroxosulfate hydrates, oxysulfates, acetates,nitrates, fluorides, fluoride hydrates, chlorides, chloride hydrates,oxychlorides, bromides, iodides, iodide hydrates, carboxylic acidderivatives and/or alkoxides.

The metal compounds preferably comprise aluminum chloride, aluminumhydroxide, aluminum nitrate, aluminum sulfate, titanyl sulfate, zincnitrate, zinc oxide, zinc hydroxide and/or zinc sulfate.

Also suitable are aluminum metal, fluoride, hydroxychloride, bromide,iodide, sulfide, selenide; phosphide, hypophosphite, antimonide,nitride; carbide, hexafluorosilicate; hydride, calcium hydride,borohydride; chlorate; sodium aluminum sulfate, aluminum potassiumsulfate, aluminum ammonium sulfate, nitrate, metaphosphate, phosphate,silicate, magnesium silicate, carbonate, hydrotalcite, sodium carbonate,borate, thiocyanate oxide, oxide hydroxide, their corresponding hydratesand/or polyaluminum hydroxy compounds, which preferably have an aluminumcontent of 9 to 40% by weight.

Also suitable are aluminum salts of mono-, di-, oligo-, polycarboxylicacids such as, for example, aluminum diacetate, acetotartrate, formate,lactate, oxalate, tartrate, oleate, palmitate, stearate,trifluoromethanesulfonate, benzoate, salicylate, 8-oxyquinolate.

Likewise suitable are elemental, metallic zinc and also zinc salts suchas for example zinc halides (zinc fluoride, zinc chlorides, zincbromide, zinc iodide).

Also suitable are zinc borate, carbonate, hydroxide carbonate, silicate,hexafluorosilicate, stannate, hydroxide stannate, magnesium aluminumhydroxide carbonate; nitrate, nitrite, phosphate, pyrophosphate;sulfate, phosphide, selenide, telluride and zinc salts of the oxoacidsof the seventh main group (hypohalites, halites, halates, for examplezinc iodate, perhalates, for example zinc perchlorate); zinc salts ofthe pseudohalides (zinc thiocyanate, zinc cyanate, zinc cyanide); zincoxides, peroxides, hydroxides or mixed zinc oxide hydroxides.

Preference is given to zinc salts of the oxoacids of transition metals(for example zinc chromate(VI) hydroxide, chromite, molybdate,permanganate).

Also suitable are zinc salts of mono-, di-, oligo-, polycarboxylicacids, for example zinc formate, acetate, trifluoroacetate, propionate,butyrate, valerate, caprylate, oleate, stearate, oxalate, tartrate,citrate, benzoate, salicylate, lactate, acrylate, maleate, succinate,salts of amino acids (glycine), of acidic hydroxyl functions (zincphenoxide etc), zinc p-phenolsulfonate, acetylacetonate, stannate,dimethyldithiocarbamate, trifluoromethanesulfonate.

In the case of titanium compounds, metallic titanium is suitable as istitanium(III) and/or (IV) chloride, nitrate, sulfate, formate, acetate,bromide, fluoride, oxychloride, oxysulfate, oxide, n-propoxide,n-butoxide, isopropoxide, ethoxide, 2-ethylhexyl oxide.

Also suitable is metallic tin and also tin salts (tin(II) and/or (IV)chloride); tin oxides and tin alkoxide such as, for example, tin(IV)tert-butoxide.

Cerium(III) fluoride, chloride and nitrate are also suitable.

In the case of zirconium compounds, metallic zirconium is preferred asare zirconium salts such as zirconium chloride, zirconium sulfate,zirconyl acetate, zirconyl chloride. Zirconium oxides and also zirconium(IV) tert-butoxide are also preferred.

The reaction in process stage c) is preferably carried out at a solidscontent of the monohydroxy-functionalized dialkylphosphinic acid saltsin the range from 0.1% to 70% by weight, preferably 5% to 40% by weight.

The reaction in process stage d) is preferably carried out at atemperature of 20 to 250° C., preferably at a temperature of 80 to 120°C.

The reaction in process stage c) is preferably carried out at a pressurebetween 0.01 and 1000 bar, preferably 0.1 to 100 bar.

The reaction in process stage c) preferably takes place during areaction time in the range from 1*10⁻⁷ to 1000 h.

Preferably, the monohydroxy-functionalized dialkylphosphinic acid salt(III) removed after process stage c) from the reaction mixture byfiltration and/or centrifugation is dried.

Preferably, the product mixture obtained after process stage b) isreacted with the metal compounds without further purification.

Preferred solvents are the solvents mentioned in process step a).

The reaction in process stage b) and/or c) is preferably carried out inthe solvent system given by stage a).

The reaction in process stage c) is preferred in a modified solventsystem. Acidic components, solubilizers, foam inhibitors, etc are addedfor this purpose.

In a further embodiment of the method, the product mixture obtainedafter process stage a) and/or b) is worked up.

In a further embodiment of the method, the product mixture obtainedafter process stage b) is worked up and thereafter themonohydroxy-functionalized dialkylphosphinic acids and/or salts oresters (III) obtained after process stage b) are reacted in processstage c) with the metal compounds.

Preferably, the product mixture after process stage b) is worked up byisolating the monohydroxy-functionalized dialkylphosphinic acids and/orsalts or esters (III) by removing the solvent system, for example byevaporation.

Preferably, the monohydroxy-functionalized dialkylphosphinic acid salt(III) of the metals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe selectively hasa residual moisture content of 0.01% to 10% by weight, preferably of0.1% to 1% by weight, an average particle size of 0.1 to 2000 μm,preferably of 10 to 500 μm, a bulk density of 80 to 800 g/l, preferably200 to 700 g/l, and a Pfrengle flowability of 0.5 to 10, preferably of 1to 5.

The molded articles, films, threads and fibers more preferably containfrom 5% to 30% by weight of the monohydroxy-functionalizeddialkylphosphinic acid/ester/salts produced according to one or more ofclaims 1 to 7, from 5% to 80% by weight of polymer or mixtures thereof,from 5% to 40% by weight of additives and from 5% to 40% by weight offiller, wherein the sum total of the components is always 100% byweight.

The additives preferably comprise antioxidants, antistats, blowingagents, further flame retardants, heat stabilizers, impact modifiers,processing aids, lubricants, light stabilizers, antidripping agents,compatibilizers, reinforcing agents, fillers, nucleus-forming agents,nucleating agents, additives for laser marking, hydrolysis stabilizers,chain extenders, color pigments, softeners, plasticizers and/orplasticizing agents.

Preference is given to a flame retardant containing 0.1 to 90% by weightof the monocarboxy-functionalized dialkylphosphinic acid, ester andsalts (III) and 0.1% to 50% by weight of further additives, morepreferably diols.

Preferred additives are also aluminum trihydrate, antimony oxide,brominated aromatic or cycloaliphatic hydrocarbons, phenols, ethers,chloroparaffin, hexachlorocyclopentadiene adducts, red phosphorus,melamine derivatives, melamine cyanurates, ammonium polyphosphates andmagnesium hydroxide. Preferred additives are also further flameretardants, more particularly salts of dialkylphosphinic acids.

More particularly, the present invention provides for the use of thepresent invention monohydroxy-functionalized dialkylphosphinic acid,esters and salts (III) as flame retardants or as an intermediate in themanufacture of flame retardants for thermoplastic polymers such aspolyesters, polystyrene or polyamide and for thermoset polymers such asunsaturated polyester resins, epoxy resins, polyurethanes or acrylates.

Suitable polyesters are derived from dicarboxylic acids and their estersand diols and/or from hydroxycarboxylic acids or the correspondinglactones. It is particularly preferable to use terephthalic acid andethylene glycol, 1,3-propanediol and 1,3-butanediol.

Suitable polyesters include inter alia polyethylene terephthalate,polybutylene terephthalate (Celanex® 2500, Celanex® 2002, from Celanese;Ultradur®, from BASF), poly-1,4-dimethylolcyclohexane terephthalate,polyhydroxybenzoates, and also block polyether esters derived frompolyethers having hydroxyl end groups; and also polyesters modified withpolycarbonates or MBS.

Synthetic linear polyesters having permanent flame retardancy arecomposed of dicarboxylic acid components, diol components of the presentinvention monohydroxy-functionalized dialkylphosphinic acids and ester,or of the monohydroxy-functionalized dialkylphosphinic acids and estersproduced by the method of the present invention as phosphorus-containingchain members. The phosphorus-containing chain members account for 2-20%by weight of the dicarboxylic acid component of the polyester. Theresulting phosphorus content in the polymer is preferably 0.1-5% byweight, more preferably 0.5-3% by weight.

The following steps can be carried out with or by addition of thecompounds produced according to the present invention.

Preferably, the molding material is produced from the free dicarboxylicacid and diols by initially esterifying directly and thenpolycondensing.

When proceeding from dicarboxylic esters, more particularly dimethylesters, it is preferable to first transesterify and then to polycondenseby using catalysts customary for this purpose.

Polyester production may preferably proceed by adding customaryadditives (crosslinking agents, matting agents and stabilizing agents,nucleating agents, dyes and fillers, etc) in addition to the customarycatalysts.

The esterification and/or transesterification involved in polyesterproduction is preferably carried out at temperatures of 100-300° C.,more preferably at 150-250° C.

The polycondensation involved in polyester production preferably takesplace at pressures between 0.1 to 1.5 mbar and temperatures of 150-450°C., more preferably at 200-300° C.

The flame-retardant polyester molding materials produced according tothe present invention are preferably used in polyester molded articles.

Preferred polyester molded articles are threads, fibers, self-supportingfilms/sheets and molded articles containing mainly terephthalic acid asdicarboxylic acid component and mainly ethylene glycol as diolcomponent.

The resulting phosphorus content in threads and fibers produced fromflame-retardant polyesters is preferably 0.1%-18%, more preferably0.5%-15% by weight and in the case of self-supporting films/sheets0.2%-15%, preferably 0.9%-12% by weight.

Suitable polystyrenes are polystyrene, poly(p-methylstyrene) and/orpoly(alpha-methylstyrene).

Suitable polystyrenes preferably comprise copolymers of styrene oralpha-methylstyrene with dienes or acrylic derivatives, for examplestyrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate,styrene-butadiene-alkyl acrylate and styrene-butadiene-alkylmethacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methylacrylate; mixtures of high impact strength from styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene-propylene-diene terpolymer; also block copolymers of styrene,for example styrene-butadiene-styrene, styrene-isoprene-styrene,styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

Suitable polystyrenes preferably also comprise graft copolymers ofstyrene or alpha-methylstyrene, for example styrene on polybutadiene,styrene on polybutadiene-styrene or polybutadiene-acrylonitrilecopolymers, styrene and acrylonitrile (or methacrylonitrile) onpolybutadiene; styrene, acrylonitrile and methyl methacrylate onpolybutadiene; styrene and maleic anhydride on polybutadiene; styrene,acrylonitrile and maleic anhydride or maleimide on polybutadiene;styrene and maleimide on polybutadiene, styrene and alkyl acrylates oralkyl methacrylates on polybutadiene, styrene and acrylonitrile onethylene-propylene-diene terpolymers, styrene and acrylonitrile onpoly(alkyl acrylate)s or poly(alkyl methacrylate)s, styrene andacrylonitrile on acrylate-butadiene copolymers, and also their mixtures,as are also known for example as ABS, MBS, ASA or AES polymers.

The polymers preferably comprise polyamides and copolyamides derivedfrom diamines and dicarboxylic acids and/or from aminocarboxylic acidsor the corresponding lactams, such as nylon-2,12, nylon-4, nylon-4,6,nylon-6, nylon-6,6, nylon-6,9, nylon-6,10, nylon-6,12, nylon-6,66,nylon-7,7, nylon-8,8, nylon-9,9, nylon-10,9, nylon-10,10, nylon-11,nylon-12, and so on. Such polyamides are known for example under thetrade names Nylon®, from DuPont, Ultramid®, from BASF, Akulon® K122,from DSM, Zytel® 7301, from DuPont; Durethan® B 29, from Bayer andGrillamid®, from Ems Chemie.

Also suitable are aromatic polyamides proceeding from m-xylene, diamineand adipic acid; polyamides produced from hexamethylenediamine and iso-and/or terephthalic acid and optionally an elastomer as modifier, forexample poly-2,4,4-trimethylhexamethyleneterephthalamide orpoly-m-phenyleneisophthalamide, block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers or with polyethers, for example withpolyethylene glycol, polypropylene glycol or polytetramethylene glycol.Also EPDM- or ABS-modified polyamides or copolyamides; and alsopolyamides condensed during processing (“RIM polyamide systems”).

The monohydroxy-functionalized dialkylphosphinic acid/ester/saltsproduced according to one or more of claims 1 to 7 are preferably usedin molding materials further used for producing polymeric moldedarticles.

It is particularly preferable for the flame-retardant molding materialto contain from 5% to 30% by weight of monohydroxy-functionalizeddialkylphosphinic acids, salts or esters produced according to one ormore of claims 1 to 7, from 5% to 80% by weight of polymer or mixturesthereof, from 5% to 40% by weight of additives and 5% to 40% by weightof filler, wherein the sum total of the components is always 100% byweight.

The present invention also provides flame retardants containingmonohydroxy-functionalized dialkylphosphinic acids, salts or estersproduced according to one or more of claims 1 to 7.

The present invention also provides polymeric molding materials and alsopolymeric molded articles, films, threads and fibers containing themonohydroxy-functionalized dialkylphosphinic acid salts (III) of themetals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe produced according to thepresent invention.

The examples which follow illustrate the invention.

Production, processing and testing of flame-retardant polymeric moldingmaterials and flame-retardant polymeric molded articles.

The flame-retardant components are mixed with the polymeric pellets andany additives and incorporated on a twin-screw extruder (Leistritz LSM®30/34) at temperatures of 230 to 260° C. (glassfiber-reinforced PBT) orof 260 to 280° C. (glassfiber-reinforced PA 66). The homogenizedpolymeric strand was hauled off, water bath cooled and then pelletized.

After sufficient drying, the molding materials were processed on aninjection molding machine (Aarburg Allrounder) at melt temperatures of240 to 270° C. (glassfiber-reinforced PBT) or of 260 to 290° C.(glassfiber-reinforced PA 66) to give test specimens. The test specimensare subsequently flammability tested and classified using the UL 94(Underwriter Laboratories) test.

UL 94 (Underwriter Laboratories) fire classification was determined ontest specimens from each mixture, using test specimens 1.5 mm inthickness.

The UL 94 fire classifications are as follows:

V-0 afterflame time never longer than 10 sec, total of afterflame timesfor 10 flame applications not more than 50 sec, no flaming drops, nocomplete consumption of the specimen, afterglow time for specimens neverlonger than 30 sec after end of flame application.

V-1 afterflame time never longer than 30 sec after end of flameapplication, total of afterflame time for 10 flame applications not morethan 250 sec, afterglow time for specimens never longer than 60 secafter end of flame application, other criteria as for V-0

V-2 cotton indicator ignited by flaming drops, other criteria as for V-1not classifiable (ncl): does not comply with fire classification V-2.

Some investigated specimens were also tested for their LOI value. TheLOI (Limiting Oxygen Index) value is determined according to ISO 4589.According to ISO 4589, the LOI is the lowest oxygen concentration involume percent which in a mixture of oxygen and nitrogen will supportcombustion of the plastic. The higher the LOI value, the greater theflammability resistance of the material tested.

LOI   23 flammable LOI 24-28 potentially flammable LOI 29-35 flameresistant LOI >36 particularly flame-resistant

Chemicals and abbreviations used

-   -   VE water completely ion-free water    -   AIBN azobis(isobutyronitrile), (from WAKO Chemicals GmbH)    -   WakoV65 2,2′-azobis(2,4-dimethylvaleronitrile), (from WAKO        Chemicals GmbH)    -   Deloxan® THP II metal scavenger (from Evonik Industries AG)

EXAMPLE 1

At room temperature, a three-neck flask equipped with stirrer andhigh-performance condenser is initially charged with 188 g of water andthis initial charge is devolatilized by stirring and passing nitrogenthrough it. Then, under nitrogen, 0.2 mg of palladium(II) sulfate and2.3 mg of tris(3-sulfophenyl)phosphine trisodium salt are added, themixture is stirred, and then 66 g of phosphinic acid in 66 g of waterare added. The reaction solution is transferred to a 2 l Büchi reactorand charged with ethylene under superatmospheric pressure while stirringand the reaction mixture is heated to 80° C. After 28 g of ethylene hasbeen taken up, the system is cooled down and free ethylene isdischarged. The reaction mixture is freed of solvent on a rotaryevaporator. The residue is admixed with 100 g of VE water, then filteredand the filtrate is extracted with toluene, thereafter freed of solventon a rotary evaporator and the resulting ethylphosphonous acid (92 g(98% of theory)) is collected.

EXAMPLE 2

Example 1 is repeated with 99 g of phosphinic acid, 396 g of butanol, 42g of ethylene, 6.9 mg of tris(dibenzylideneacetone)dipalladium and 9.5mg of 4,5-bis-(diphenylphosphino)-9,9-dimethylxanthene, for purificationover a column charged with Deloxan® THP II and the further addition ofn-butanol. At a reaction temperature of 80-110° C., the water formed isremoved by azeotropic distillation. The product (butyl ethylphosphonite)is purified by distillation at reduced pressure. Yield: 189 g (84% oftheory).

EXAMPLE 3

Example 1 is repeated with 198 g of phosphinic acid, 198 g of water, 84g of ethylene, 6.1 mg of palladium(II) sulfate and 25.8 mg of9,9-dimethyl-4,5-bis-(diphenylphosphino)-2,7-sulfonatoxanthene disodiumsalt, for purification over a column charged with Deloxan® THP II andthe further addition of n-butanol. At a reaction temperature of 80-110°C., the water formed is removed by azeotropic distillation. The product(butyl ethylphosphonite) is purified by distillation at reducedpressure. Yield: 374 g (83% of theory).

EXAMPLE 4

A 500 ml five-neck flask equipped with gas inlet tube, thermometer,high-performance stirrer and reflux condenser with gas incineration ischarged with 94 g (1 mol) of ethylphosphonous acid (produced as inExample 1). Ethylene oxide is introduced at room temperature. A reactiontemperature of 70° C. is set with cooling, followed by further reactionat 80° C. for one hour. The ethylene oxide takeup is 65.7 g. The acidnumber of the product is less than 1 mg KOH/g. Yield: 129 g (94% oftheory) of 2-hydroxyethyl ethylphosphonite as colorless, water-clearproduct.

EXAMPLE 5

4.5 g (30 mmol) of butyl ethylphosphonite (produced as in Example 3) aredissolved in 30 ml of toluene and admixed at −78° C. with 12 ml (30mmol) of a 2.5 molar solution of butyllithium in hexane. After stirringfor 15 minutes 5.68 g (40 mmol) of boron trifluoride etherate are addedand ethylene oxide is passed in followed by further reaction for twohours. Then, aqueous ammonium chloride solution is added followed bywarming to room temperature. This is followed by concentrating in vacuo,taking up in diethyl ether, removal of insoluble salts by filtration andrenewed concentrating. Chromatographic purification leaves 4.2 g (73% oftheory) of butyl ethyl(2-hydroxyethyl)phosphinate as oil.

EXAMPLE 6

4.5 g (30 mmol) of butyl ethylphosphonite (produced as in Example 2) aredissolved in 30 ml of toluene and at 0° C. admixed with 0.72 g (30 mmol)of sodium hydride. After stirring for one hour 5.68 g (40 mmol) of borontrifluoride etherate are added and ethylene oxide is passed in followedby further reaction for two hours. Then, aqueous ammonium chloridesolution is added followed by warming to room temperature. This isfollowed by concentrating in vacuo, taking up in diethyl ether, removalof insoluble salts by filtration and renewed concentrating.Chromatographic purification leaves 4.5 g (78% of theory) of butylethyl(2-hydroxyethyl)phosphinate as oil.

EXAMPLE 7

In a stirred apparatus, 194 g (1 mol) of butylethyl(2-hydroxyethyl)phosphinate (produced as in Example 5) aredissolved in 200 ml (2 mol) of concentrated hydrochloric acid. Theefficiently stirred mixture is heated to about 90° C. and reacted atthat temperature for about 8 hours. The water is then completelydistilled off in vacuo. The residue is taken up in acetic acid andextracted. The solvent of the filtrate is removed in vacuo to obtain 143g (94% of theory) of ethyl-(2-hydroxyethyl)phosphinic acid as oil.

EXAMPLE 8

A stirred apparatus is initially charged with 150 g of butanol, 65 g ofwater, 150 g (3.75 mol) of sodium hydroxide and 242.5 g (1.25 mol) ofbutyl ethyl(2-hydroxy-ethyl)phosphinate (produced as in Example 6). Thestirred mixture is heated to about 120° C. and reacted for 6 hours.Then, 250 ml of water are added and the butanol is distilled off.Following the addition of 500 ml of water, the mixture is neutralized byaddition of about 184 g (1.88 mol) of concentrated sulfuric acid. Thewater is then distilled off in vacuo. The residue is taken up intetrahydrofuran, extracted and the insoluble salts are filtered off. Thesolvent of the filtrate is distilled off in vacuo to obtain 220 g (98%of theory) of ethyl(2-hydroxyethyl)-phosphinic acid as oil.

EXAMPLE 9

828 g (6 mol) of ethyl(2-hydroxyethyl)phosphinic acid (produced as inExample 8) are dissolved in 860 g of water and initially charged into a5 l five-neck flask equipped with thermometer, reflux condenser,high-performance stirrer and dropping funnel and neutralized with about480 g (6 mol) of 50% sodium hydroxide solution. A mixture of 1291 g of a46% aqueous solution of Al₂(SO₄)₃.14 H₂O is added at 85° C. The solidmaterial obtained is subsequently filtered off, washed with hot waterand dried at 130° C. in vacuo. Yield: 803 g (91% of theory) ofethyl-(2-hydroxyethyl)phosphinic acid aluminum(III) salt as colorlesssalt.

EXAMPLE 10

138 g (1 mol) of ethyl(2-hydroxyethyl)phosphinic acid (produced as inExample 7) and 85 g of titanium tetrabutoxide are refluxed in 500 ml oftoluene for 40 hours. The resulting butanol is distilled off from timeto time with proportions of toluene. The solution formed is subsequentlyfreed of solvent to leave 136 g (91% of theory) ofethyl(2-hydroxyethyl)phosphinic acid titanium salt.

EXAMPLE 11

414 g (3 mol) of ethyl(2-hydroxyethyl)phosphinic acid (produced as inExample 8) are at 85° C. dissolved in 400 ml of toluene and admixed with888 g (12 mol) of butanol. At a reaction temperature of about 100° C.,the water formed is removed by azeotropic distillation to leave 500 g(86% of theory) of butyl ethyl(2-hydroxyethyl)phosphinate.

EXAMPLE 12

414 g (3.0 mol) of ethyl(2-hydroxyethyl)phosphinic acid (produced as inExample 7) are at 80° C. dissolved in 400 ml of toluene and admixed with594 g (6.6 mol) of 1,4-butanediol and esterified at about 100° C. in adistillation apparatus equipped with water trap during 4 h. Oncompletion of the esterification the toluene is removed in vacuo toleave 504 g (80% of theory) of 4-hydroxybutylethyl-(2-hydroxyethyl)phosphinate as colorless oil.

EXAMPLE 13

To 388 g (2 mol) of butyl ethyl(2-hydroxyethyl)phosphinate (produced asin Example 5) are added 155 g (2.5 mol) of ethylene glycol and 0.4 g ofpotassium titanyloxalate, followed by stirring at 200° C. for 2 h.Volatiles are distilled off by gradual evacuation to leave 315 g (96% oftheory) of 2-hydroxyethyl ethyl-(2-hydroxyethyl)phosphinate.

EXAMPLE 14

A 500 ml five-neck flask equipped with gas inlet tube, thermometer,high-performance stirrer and reflux condenser with gas incineration ischarged with 138 g (1 mol) of ethyl(2-hydroxyethyl)phosphinic acid(produced as in Example 8) and ethylene oxide is passed in. A reactiontemperature of 70° C. is set, followed by further reaction for 1 h. Theethylene oxide takeup is 64.8 g. The acid number of the product is lessthan 1 mg KOH/g. 173 g (95% of theory) of 2-hydroxyethylethyl(2-hydroxyethyl)phosphinate as colorless, water-clear liquid wereobtained.

EXAMPLE 15

To 18.2 g of 2-hydroxyethyl ethyl(2-hydroxyethyl)phosphinate (producedas in Example 14) are added 290 g of terephthalic acid, 188 g ofethylene glycol and 0.34 g of zinc acetate, and the mixture is heated to200° C. for 2 h. Then, 0.29 g of trisodium phosphate anhydrate and 0.14g of antimony(III) oxide are added, followed by heating to 280° C. andsubsequent evacuation.

The melt obtained (349 g, phosphorus content 0.9%) is used to injectionmold test specimens 1.6 mm in thickness for measurement of the limitingoxygen index (LOI) to ISO 4589-2 and also for the UL 94 flammabilitytest. The test specimens thus produced gave an LOI of 40 and were UL 94classified as flammability class V-0. Corresponding test specimenswithout 2-hydroxyethyl ethyl(2-hydroxyethyl)-phosphinate gave an LOI ofjust 31 and were UL 94 classified as flammability class V-2 only. Thepolyester molded article containing 2-hydroxyethylethyl(2-hydroxyethyl)phosphinate hence clearly has flame-retardantproperties.

EXAMPLE 16

To 11.6 g of ethyl(2-hydroxyethyl)phosphinic acid (produced as inExample 7) are added to 12.9 g of 1,3-propylene glycol and at 160° C.the water formed by esterification is stripped off. Then, 378 g ofdimethyl terephthalate, 152 g of 1,3-propanediol, 0.22 g of tetrabutyltitanate and 0.05 g of lithium acetate are added and the mixture isinitially heated at 130 to 180° C. for 2 h with stirring and thereafterat 270° C. The polymer (431 g) contains 0.6% of phosphorus, the LOI is34.

EXAMPLE 17

To 11.6 g of ethyl(2-hydroxyethyl)phosphinic acid (produced as inExample 8) are added 367 g of dimethyl terephthalate, 170 g of1,4-butanediol, 0.22 g of tetrabutyl titanate and 0.05 g of lithiumacetate and the mixture is initially heated at 130 to 180° C. for 2 hwith stirring and thereafter at 270° C. The polymer (424 g) contains0.6% of phosphorus, the LOI is 34, the LOI of untreated polybutyleneterephthalate is 23.

EXAMPLE 18

In a 250 ml five-neck flask equipped with reflux condenser, stirrer,thermometer and nitrogen inlet, 100 g of a bisphenol A bisglycidyl etherhaving an epoxy value of 0.55 mol/100 g (Beckopox EP 140, from Solutia)and 17.9 g (0.13 mol) of ethyl-(2-hydroxyethyl)phosphinic acid (producedanalogously to Example 8) are heated to not more than 150° C. withstirring. A clear melt forms after 30 min. After a further hour ofstirring at 150° C., the melt is cooled down and triturated to obtain116.4 g of a white powder having a phosphorus content of 3.3% by weight.

EXAMPLE 19

In a 2 l flask equipped with stirrer, water trap, thermometer, refluxcondenser and nitrogen inlet, 29.4 g of phthalic anhydride, 19.6 g ofmaleic anhydride, 24.8 g of propylene glycol, 14.4 g of 2-hydroxyethylethyl(2-hydroxyethyl)phosphinate (produced as in Example 14), 20 g ofxylene and 50 mg of hydroquinone are heated to 100° C. while stirringand with nitrogen being passed through. The heating operation is stoppedwhen the exothermic reaction is started. After the reaction has dieddown, stirring is continued at about 190° C. After 14 g of water havebeen separated off, the xylene is distilled off and the polymer melt iscooled down. This gives 89.6 g of a white powder having a phosphoruscontent of 2.3% by weight.

EXAMPLE 20

A mixture of 50% by weight of polybutylene terephthalate, 20% by weightof ethyl-(2-hydroxyethyl)phosphinic acid aluminum(III) salt (produced asin Example 9) and 30% by weight of glass fibers are compounded on atwin-screw extruder (Leistritz LSM 30/34) at temperatures of 230 to 260°C. to form a polymeric molding material. The homogenized polymericstrand was hauled off, water bath cooled and then pelletized. Afterdrying, the molding materials are processed on an injection moldingmachine (Aarburg Allrounder) at 240 to 270° C. to form polymeric moldedarticles which achieved a UL-94 classification of V-0.

EXAMPLE 21

A mixture of 53% by weight of nylon-6,6, 30% by weight of glass fibers,17% by weight of ethyl(2-hydroxyethyl)phosphinic acid titanium salt(produced as in Example 10) are compounded on a twin-screw extruder(Leistritz LSM 30/34) to form polymeric molding materials. Thehomogenized polymeric strand was hauled off, water bath cooled and thenpelletized. After drying, the molding materials are processed on aninjection molding machine (Aarburg Allrounder) at 260 to 290° C. to formpolymeric molded articles which achieved a UL-94 classification of V-0.

What is claimed is:
 1. A method for producing monohydroxy-functionalizeddialkylphosphinic acids, esters or salts thereof comprising the stepsof: a) reacting a phosphinic acid source (I)

with olefins (IV)

in the presence of a catalyst A to form an alkylphosphonous acid, saltor ester (II)

b) reacting the alkylphosphonous acid, salt or ester (II) with at leastone alkylene oxide (V), wherein the at least one alkylene oxide isethylene oxide, 1,2-propylene oxide or 2,3-epoxy-1propanol

in the presence of a catalyst B and at least one base to formmonofunctionalized dialkylphosphinic acid derivative (III)

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ are identical or different and areindependently H, CH₂OH, methyl or ethylene, wherein X is Mg, Ca, Al, Sb,Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Na, K, H, a protonatednitrogen base or a combination thereof and the catalyst A is selectedfrom the group consisting of a transition metal, transition metalcompound and catalyst systems composed of a transition metal, transitionmetal compound or a combination thereof and at least one ligand, and thecatalyst B is a Lewis acid and wherein the bases used in process step b)are metals, metal hydrides, organometal compounds or metal alkoxides. 2.The method according to claim 1 wherein the monohydroxy-functionalizeddialkylphosphinic acid, its salt or ester (III) obtained after step b)is reacted in a step c) with a metal compound, a protonated nitrogenbase or a combination thereof, wherein the metal compound contains themetal Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na orK to form the monohydroxy-functionalized dialkylphosphinic acid salts(III) of the metal compound, of the nitrogen base or a combinationthereof.
 3. The method according to claim 1 wherein the alkylphosphonousacid, salt or ester (II) obtained after step a), or themonohydroxy-functionalized dialkylphosphinic acid, salt or ester (III)obtained after step b), is esterified with an alkylene oxide or an orbranched, saturated or unsaturated, monohydric or polyhydric organicalcohol having a carbon chain length of C₁-C₁₈, or a combinationthereof, and the resulting alkylphosphonous ester (II) ormonohydroxy-functionalized dialkylphosphinic ester (III) are subjectedto the further reaction step b).
 4. The method according to claim 1,wherein X is H, C Mg, Al Zn, Ti, Fe, Ce, or a combination thereof. 5.The method according to claim 1, wherein the transition metal or thetransition metal in the transition metal compound is selected from thefirst, seventh or eighth transition groups.
 6. The method according toclaim 1, wherein the transition metal or the metal of the transitionmetal compound is rhodium, nickel, palladium, platinum or ruthenium. 7.The process as claimed in claim 1, wherein the base of the process isselected from lithium, lithium hydride, lithium aluminohydride,methyllithium, butyllithium, t-butyllithium, lithium diisopropylamide,sodium, sodium hydride, sodium methoxide, sodium ethoxide, sodiumbutoxide, potassium methoxide, potassium ethoxide or potassium butoxide.